CN111675978A - Transfer laminated medium and printed matter - Google Patents
Transfer laminated medium and printed matter Download PDFInfo
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- CN111675978A CN111675978A CN202010529196.9A CN202010529196A CN111675978A CN 111675978 A CN111675978 A CN 111675978A CN 202010529196 A CN202010529196 A CN 202010529196A CN 111675978 A CN111675978 A CN 111675978A
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- Prior art keywords
- fine uneven
- uneven structure
- resin
- transfer
- film
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
- B32B37/025—Transfer laminating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/75—Printability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2551/00—Optical elements
Abstract
The invention provides a transfer laminated medium (1) which can produce printed matter containing a micro uneven structure body with high yield. The transfer laminate medium is a transfer laminate medium capable of forming a transfer laminate on a transfer target by hot stamping, the transfer laminate including a fine uneven structure portion having a fine uneven shape, and the transfer laminate medium is characterized by comprising: the transfer sheet comprises a support base material (2), a bonding layer (3) formed on the support base material, a fine uneven structure portion (4) having a fine uneven shape formed on the bonding layer, and an adhesive layer (6) formed on the fine uneven structure portion, wherein the fine uneven structure portion is formed separately at intervals so as to be capable of being internally wrapped in an area to be transferred by hot stamping.
Description
The present application is a divisional application having an application number of 201480030804.4, an application date of 2014, 5/30, and an invention name of "transfer laminated medium and printed matter".
Technical Field
The present invention relates to a transfer laminate medium and a printed matter, and more particularly, to a transfer laminate medium for thermally transferring a printed matter or the like having a transfer laminate containing a fine uneven structure by hot stamping.
Background
In the case of continuously replicating a large number of fine uneven patterns on a transfer laminate medium, typical methods include an "imprint method" described in patent document 1, a "casting method" described in patent document 2, and a "photopolymer method" described in patent document 3.
In the case of producing a fine uneven structure by the "imprint method", the shape of the fine uneven structure is transferred by heating the resin layer on the side where the fine uneven structure is formed to a softening point or higher and pressing the resin layer against a relief mold (a mold for transferring the fine uneven structure). As another method, there is a method of pressing a relief mold itself heated to a softening point of the resin layer or higher against the resin layer to transfer the shape of the fine uneven structure. In either method, it is necessary to set the processing temperature of the resin layer on the side where the fine uneven structure is formed to a temperature equal to or higher than the softening point thereof. The heat-resistant temperature of the formed uneven microstructure is almost equal to the minimum processing temperature.
As a result, in order to obtain a fine uneven structure having high heat resistance, it is necessary to use a resin having a softening point equal to or higher than a desired heat-resistant temperature and perform molding at a high processing temperature equal to or higher than the desired heat-resistant temperature, and therefore, high heat is required, the processing speed is low, and productivity is lowered.
In the case of producing a fine uneven structure by the "casting method", a resin for forming the fine uneven structure is heated to a melting point or higher, and is melt-extruded on a relief mold (a mold for transferring the fine uneven structure) to transfer the shape of the fine uneven structure, and after the resin is cooled to lower the fluidity, the resin is peeled off from the relief mold.
In this case, a processing temperature equal to or higher than the melting point of the resin for forming the fine uneven structure is also required. The heat-resistant temperature of the formed uneven microstructure is almost equal to the minimum processing temperature.
The "photopolymer method" (2P method, photosensitive resin method) is described in, for example, patent document 3, and a high-definition fine relief pattern can be obtained by a method in which a radiation-curable resin is poured between a "relief mold (mold for transferring a fine relief pattern)" and a "flat substrate (plastic film or the like)" and cured by radiation, and then the cured film is peeled off from the "relief mold" together with the substrate.
The optical element obtained by this method has a good accuracy of forming the uneven pattern and is excellent in heat resistance and chemical resistance as compared with the "imprint method" or "casting method" using a thermoplastic resin. Further, since the liquid radiation curable resin is used, heat is not required for processing.
However, the following problems are present in any of the molding methods such as the "imprint method", the "casting method", and the "photopolymer method". This will be explained with reference to fig. 7. In fig. 7, reference numeral 101 denotes a transfer laminated medium. The transfer laminate medium 101 has a structure in which a bonding layer 103, a fine uneven structure forming layer 104, a reflection layer 105, and an adhesive layer 106 are laminated in this order on a supporting base 102.
In the molding method using the transfer laminated medium 101, the fine uneven structure forming layer 104 made of a resin for forming a transfer region including the fine uneven structure on the object to be transferred is a continuous layer as shown in fig. 7. Therefore, in the transfer step by hot stamping of the transfer laminated medium 101, the fine uneven structure forming layer 104 is melted and broken in the region to be transferred, and a desired fine uneven structure is transferred to the object to be transferred via the adhesive layer 106. As a result, since the fracture properties of the transfer laminated medium 101 including the fine uneven structure forming layer 104 depend on the fracture strength of the resin used in the fine uneven structure forming layer 104, for example, when thermal transfer is performed at a position indicated by a dotted line in fig. 7, transfer burrs or transfer defects occur, resulting in a reduction in the yield.
Fig. 8 illustrates the occurrence of such transfer burrs or transfer defects when transferring with the conventional transfer laminated medium 101. That is, in the vicinity of the boundary portion between the pressure bonded region and the non-pressure region shown in the region a of fig. 8, as shown in the region a' of fig. 8, transfer burrs or transfer defects are generated in the peeling step.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4194073
Patent document 2: utility model registration No. 524092
Patent document 3: japanese patent No. 4088884
Patent document 4: japanese laid-open patent publication No. 2000-211927
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a transfer laminate medium that has fine uneven structure portions formed individually at intervals so as to be able to wrap in a region to be transferred by hot stamping, and that has good transferability without being affected by the heat resistance, hardness, flexibility, and other fracture properties of the resin used for the fine uneven structure portions.
Further, it is preferable that the fine uneven structure portion is further covered with an adhesive layer and a filling portion of the same resin as the adhesive layer, whereby even if the hardness of the resin used for the fine uneven structure portion is increased, a resin having a high hardness is used only for the optical structure portion, and thus a crack of the fine uneven structure portion due to a pressure difference between a pressurized region and a non-pressurized region at the time of stamping is prevented.
Further, it is preferable that the resin used for the fine uneven structure portion or the adhesive layer is soft and has a high elongation, and even in an optical element requiring high impact resistance, the resin having high flexibility is used only for the optical structure portion, thereby preventing burrs at the time of transfer.
Means for solving the problems
In order to solve the above-described problems, the present invention provides a transfer laminate medium capable of forming a transfer laminate including a fine uneven structure portion having a fine uneven shape by hot stamping on a transfer target body, the transfer laminate medium including:
a supporting substrate,
A bonding layer formed on the supporting substrate,
A fine uneven structure portion having a fine uneven shape on the adhesive layer, and
an adhesive layer formed on the fine uneven structure part, wherein
The fine uneven structure portion is formed separately at intervals so as to be included in an area to be transferred by hot stamping.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a transfer laminate medium which has fine uneven structure portions formed individually at intervals so as to be able to be enclosed in a region to be transferred by hot stamping, has good fracture properties without being affected by the fracture properties such as heat resistance and hardness of a resin used for the fine uneven structure portions, can prevent transfer burrs or transfer defects from occurring in the fine uneven structure portions during thermal transfer, and can improve the yield.
Further, it is preferable that the uneven microstructure portion is further covered with an adhesive layer and a filling portion of the same resin as the adhesive layer, whereby even if the hardness of the resin used for the uneven microstructure portion is increased, cracks in the uneven microstructure portion can be prevented.
Further, it is preferable that the resin used for the fine uneven structure portion or the adhesive layer has high elongation and is flexible, and even in an optical element requiring high impact resistance, the resin having high flexibility can be used only for the optical structure portion, whereby burrs can be prevented at the time of transfer.
Drawings
FIG. 1 is a schematic cross-sectional view of a transfer laminate medium according to an embodiment.
FIG. 2 is a schematic cross-sectional view of another transfer laminated medium according to the embodiment.
FIG. 3 is a schematic cross-sectional view showing an example of a method for producing a fine uneven structure portion of a transfer laminate medium according to the embodiment.
FIG. 4 is a schematic cross-sectional view of the main portion of FIG. 3.
FIG. 5 is a schematic cross-sectional view for explaining the operation of the transfer laminated medium according to the embodiment.
FIG. 6 is a schematic cross-sectional view for explaining transfer using the transfer laminated medium according to the embodiment.
FIG. 7 is a conceptual sectional view for explaining problems of a conventional transfer laminated medium.
Fig. 8 is a schematic cross-sectional view for explaining transfer using a conventional transfer laminated medium.
Detailed Description
The present embodiment will be described in detail below with reference to the drawings.
Fig. 1 is a conceptual sectional view showing a configuration of a transfer laminated medium according to an embodiment. The transfer laminate medium 1 has a form in which a bonding layer 3, a fine uneven structure portion 4, a reflection layer 5, and an adhesive layer 6 are provided in this order on a support base material 2, and the fine uneven structure portion 4 is formed separately at intervals so as to be able to be included in an area to be transferred by hot stamping, and has a fine uneven shape.
The transfer laminated medium according to the embodiment can be produced by using a molding film in which a mold corresponding to the fine uneven structure portion is formed. That is, after forming the fine uneven structure portion by partially applying the molding resin ink to the surface of the molding film on which the mold is formed, the fine uneven structure portion is transferred to the adhesive layer of the transfer support base material, and the fine uneven structure portion is formed separately with a space. Next, a reflective layer may be deposited on the fine textured structure portion, and an adhesive may be further applied to form an adhesive layer and a filling portion.
That is, the fine uneven structure portion 4 is not a layer continuously formed on the surface of the adhesive layer 3, but is formed independently in 1 to a plurality of fine uneven structure portions as final shapes at desired intervals.
Further, since the fine uneven structure portion 4 is formed separately at intervals so as to be included in the region to be transferred, the transfer can be performed so that the outer periphery of the fine uneven structure portion to be transferred is positioned inside the outer periphery of the region to be transferred using the hot stamping.
The filling-in portions 7 are provided between the fine textured portions 4. The buried portion 7 is made of the same material as the adhesive layer 6. Here, "between the fine uneven structure portions 4" means between these fine uneven structure portions when a plurality of fine uneven structure portions are formed individually, but means portions adjacent to the left and right of the fine uneven structure portions when only 1 fine uneven structure portion is formed.
The reflective layer 5 is formed on the surface of the adhesive layer 3 including the fine textured structure portion 4.
Fig. 2 is a conceptual sectional view showing the structure of another transfer laminated medium according to the embodiment. The transfer laminated medium 1 has a form in which a bonding layer 3, a fine uneven structure portion 4, a reflection layer 5, a mask layer 8, and an adhesive layer 6 are provided in this order on a support base 2, and the fine uneven structure portion 4 is formed separately at intervals so as to be able to be included in a region to be transferred by hot stamping, and has a fine uneven shape. The reflective layer 5 is formed on the uneven surface of the fine uneven structure portion 4, and the mask layer 8 is formed on the reflective layer 5. That is, on the reflective layer 5 shown in fig. 1, as shown in fig. 2, the mask layer 8 is formed on a part of the reflective layer 5 corresponding to the uneven surface of the fine uneven structure portion 4, and the exposed part of the reflective layer 5 is selectively removed using the mask layer 8 as a mask, whereby the reflective layer 5 and the mask layer 8 in the arrangement state shown in fig. 2 can be formed.
The layers of fig. 1 and 2 will be described in detail below.
(supporting base Material)
In fig. 1 and 2, the support substrate 2 is preferably a film substrate. For example, plastic films such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), and PP (polypropylene) can be used as the film base material. In particular, a substrate having heat resistance that is not deformed or deteriorated by heat applied during curing and transfer is preferably used.
The surface of the support base material 2 on the side of the adhesive layer 3 is preferably subjected to a treatment for improving peelability.
(laminating layer)
In fig. 1 and 2, the adhesive layer 3 is used to smoothly transfer the fine uneven structure portion 4 during thermal transfer. The adhesive layer 3 is preferably made of an adhesive resin. Examples of the adhesive resin include thermoplastic resins such as polyester resins, acrylic resins, vinyl chloride resins, vinyl resins, polyamide resins, polyvinyl acetate resins, rubber resins, ethylene-vinyl acetate copolymer resins, and vinyl chloride-vinyl acetate copolymer resins. The adhesive layer 3 preferably has a thickness of 1 μm to 20 μm.
The adhesive layer 3 is formed of a material that also functions as a release layer at the time of transfer.
(fine uneven structure portion)
In fig. 1 and 2, the fine uneven structure portion 4 may be a relief hologram, a diffraction grating, a sub-wavelength grating, a microlens, a polarizing element, a fresnel lens plate or a lenticular lens plate used for a fluorescent screen, or the like, a backlight and a diffuser plate of a liquid crystal device, an antireflection film, or the like.
The fine uneven structure portion 4 may be formed of a thermoplastic resin, a thermosetting resin, an oxidative polymerizable resin, a reactive curable resin, an ultraviolet or electron beam curable resin, or the like. Examples of the thermoplastic resin include acrylic resins, epoxy resins, cellulose resins, polyester resins, vinyl resins, rubber resins, polyamide resins, polyimide resins, polycarbonate resins, and liquid crystals.
(formation of fine uneven Structure portion)
The fine uneven structure portion can be formed by the following method using a forming film in which a die corresponding to the fine uneven structure portion is formed, for example.
The fine uneven structure portion is formed by partially applying a molding resin ink to the surface of the molding film on which the mold is formed. Thereafter, the fine uneven structure portion may be transferred onto a bonding layer of a transfer support base material to form a fine uneven structure portion separately formed with an interval.
In the molding method, the resin used for the fine uneven structure portion is preferably a polyurethane resin or an epoxy resin which is slowly cured at normal temperature.
Polyurethane resins are generally synthesized by reacting an "isocyanate-reactive compound" with a diisocyanate, which is predominantly a difunctional "isocyanate". Functional groups such as carboxyl and amino groups may be used in combination to produce products having a wide variety of properties.
The term "isocyanate-reactive compound" as used herein includes: an optional organic compound having at least 2 isocyanate-reactive moieties, such as a compound containing an active hydrogen component, or an imino-functional compound. The active hydrogen-containing moiety means a moiety containing a hydrogen atom, and the hydrogen molecule shows a significant activity according to the Zerewitnoff test described in "Journal of the American Chemical Society, Vol.49, p.3181 (1927)" (Wohler, Japan) depending on the position in the molecule. Examples of such active hydrogen moieties are-COOH, -OH, -NH2、-NH-，-CONH2-SH and-CONH-. Preferred active hydrogen-containing compounds include polyols, polyamines, polymercaptans and polyacids. Preferred imino-functional compounds are compounds having at least 1 terminal imino group per molecule. Preferably the isocyanate-reactive compound is a polyol, more preferably a polyether polyol.
Preferred polyols include compounds containing at least 2 hydroxyl groups. These materials may be monomers, oligomers, polymers and mixtures thereof. Examples of hydroxy-functional oligomers and monomers are castor oil, trimethylolpropane and glycols. Also, branched diols such as 2-butylethyl-1, 3-propanediol and the like described in International patent application publication No. 98/053013 can be mentioned.
Examples of preferred polymers include polyester polyols, polyacrylate polyols, polycarbonate polyols, polyurethane polyols, melamine polyols, and mixtures and composites thereof. Such polymers are generally known to those skilled in the art and are commercially available. Preferred polyester polyols, polyacrylate polyols, and mixtures thereof are described, for example, in international patent application publication No. 96/20968 and european patent application publication No. 0688840. Examples of preferred polyurethane polyols are described in international patent application publication No. 96/040813.
Hydroxyl-functional epoxy resins, alkyds, and dendritic polyols include, for example, those described in international patent application publication No. 93/17060. The coating composition may comprise a latent hydroxyl functional compound, such as a compound containing a bicyclic orthoester, a spiro orthoester, a group of spiro orthosilicate, or a bicyclic amide acetal. These compounds and methods of using the same are described in international patent application publication No. 97/31073, international patent application publication No. 2004/031256, and international patent application publication No. 2005/035613, respectively.
The fine textured part may contain a metal-based catalyst for addition reaction of an isocyanate group and an isocyanate-reactive compound. Such catalysts are known to those skilled in the art. The catalyst is generally used in an amount of 0.001 to 10 wt%, preferably 0.002 to 5 wt%, more preferably 0.01 to 1 wt%, calculated as non-volatile matter per coating composition. Preferred metals in the metal-based catalyst include zinc, cobalt, manganese, zirconium, bismuth and tin. The coating composition preferably comprises a tin-based catalyst. Well-known examples of tin-based catalysts are dimethyltin dilaurate, dimethyltin di-t-carbonate, dimethyltin dioleate, dibutyltin dilaurate, dioctyltin dilaurate and stannous octoate.
On the other hand, epoxy resins are a general term for thermosetting resins that can be cured by graft polymerization of epoxy groups remaining in a polymer. The prepolymer before graft polymerization and the curing agent are mixed and subjected to a heat curing treatment.
As for the composition of the prepolymer, there are various compositions, but the most representative is a copolymer of bisphenol a and epichlorohydrin. Various polyamines or anhydrides may be used as the curing agent.
Examples of the alicyclic epoxy compound include 2- (3, 4-epoxy) cyclohexyl-5, 5-spiro- (3, 4-epoxy) cyclohexane-m-dioxane, 3, 4-epoxycyclohexyl-3 ', 4' -epoxycyclohexanecarboxylate (EECH), 3, 4-epoxycyclohexylalkyl-3 ', 4' -epoxycyclohexanecarboxylate, 3, 4-epoxy-6-methylcyclohexylmethyl 3 ', 4-epoxy-6' -methylcyclohexanecarboxylate, vinylcyclohexane dioxide, bis (3, 4-epoxycyclohexylmethyl) adipate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, exo-bis (2, 3-epoxycyclopentyl) ether, endo-exo-bis (2, 3-epoxycyclopentyl) ether, 2-bis (4- (2, 3-epoxypropoxy) cyclohexyl) propane, 2, 6-bis (2, 3-epoxypropoxycyclohexyl-p-dioxane (dioxane), 2, 6-bis (2, 3-epoxypropoxy) norbornene (norbonene), the diglycidyl ether of linoleic acid dimer, limonene dioxide, 2-bis (3, 4-epoxycyclohexyl) propane, dicyclopentadiene dioxide, 1, 2-epoxy-6- (2, 3-epoxypropoxy) hexahydro-4, 7-methyleneindane, p- (2, 3-epoxy) cyclopentylphenyl-2, 3-epoxypropyl ether, 1- (2, 3-epoxypropoxy) phenyl-5, 6-epoxyhexahydro-4, 7-methyleneindane, o- (2, 3-epoxy) cyclopentenylphenyl-2, 3-epoxypropyl ether), 1, 2-bis [5- (1, 2-epoxy) -4, 7-hexahydromethyleneindanoxy ] ethane, cyclopentenylphenylglycidyl ether, cyclohexanediol diglycidyl ether, diglycidyl hexahydrophthalate, and mixtures thereof, but is not limited thereto.
Examples of the aromatic epoxy resin include bisphenol-a epoxy resin, bisphenol-F epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, bisphenol epoxy resin, biphenyl epoxy resin, 4' -biphenyl epoxy resin, divinylbenzene dioxide resin, 2-glycidylphenylglycidyl ether resin, and the like, and mixtures thereof, but are not limited thereto.
Examples of the curing agent to be cured with the epoxy prepolymer include, but are not limited to, acid anhydrides such as maleic anhydride and maleic anhydride copolymers, amine compounds such as dicyandiamide, and phenol compounds such as phenol and resol. The curing accelerator for epoxy resins can be used, and examples thereof include imidazoles and derivatives thereof, tertiary amines, quaternary ammonium salts, and the like, but are not limited thereto.
(Molding of fine uneven Structure portion Using photo-curing Material)
The fine uneven structure portion can be formed by curing the resin by irradiation with radiation.
Examples of the radiation curable resin include monomers, oligomers, polymers, and the like having an ethylenically unsaturated bond. Examples of the monomer include: 1, 6-hexanediol, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like. Examples of the oligomer include epoxy acrylate, urethane acrylate, and polyester acrylate. Examples of the polymer include urethane-modified acrylic resins and epoxy-modified acrylic resins.
Examples of other photocurable resins include those described in Japanese patent application laid-open Nos. 61-98751, 63-23909, 63-23910 and 2007-118563. Polymers having no reactivity, such as acrylic resin, polyester resin, polyurethane resin, and epoxy resin, may be added to form a fine relief pattern shape accurately.
In the case of photo cation polymerization, monomers, oligomers, polymers, oxetane skeleton-containing compounds, vinyl ethers having an epoxy group can be used. When the ionizing radiation curable resin is cured by light such as ultraviolet light, a photopolymerization initiator may be added. The photo radical polymerization initiator, photo cation polymerization initiator, and a combination type (mixed type) thereof may be selected depending on the resin.
Examples of the photo radical polymerization initiator include benzoin-based compounds such as benzoin, benzoin methyl ether, and benzoin ethyl ether; anthraquinone compounds such as anthraquinone and methylanthraquinone; phenylketone compounds such as acetophenone, diethoxyacetophenone, benzophenone, hydroxyacetophenone, 1-hydroxycyclohexylphenylketone, α -aminoacetophenone, and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one; benzyl dimethyl ketal, thioxanthone, acyl phosphine oxide, michelson ketone, and the like.
When a compound capable of cationic photopolymerization is used, an aromatic diazonium salt, an aromatic iodonium salt, an aromatic sulfonium salt, an aromatic phosphonium salt, a mixed ligand metal salt, or the like can be used as the cationic photopolymerization initiator. When a so-called mixed type material in which photo radical polymerization and photo cation polymerization are used in combination is used, the respective polymerization initiators may be mixed and used. Aromatic iodonium salts, aromatic sulfonium salts, and the like having a function of initiating polymerization of both with one initiator can also be used.
The fine uneven structure portion is obtained by blending 0.1 to 15 mass% of a photopolymerization initiator with respect to the radiation curable resin. In the resin composition, a sensitizing dye may be used in combination with a photopolymerization initiator. If necessary, dyes, pigments, various additives (polymerization inhibitors, leveling agents, antifoaming agents, anti-sagging agents, adhesion improving agents, coating surface modifying agents, plasticizers, nitrogen-containing compounds, etc.), crosslinking agents (e.g., epoxy resins, etc.), and the like may be contained. To improve moldability, a non-reactive resin may be added.
The thickness of the fine uneven structure portion may be appropriately selected within a range of 0.1 μm to 10 μm.
Although depending on the viscosity (fluidity) of the uncured coating film, when the thickness of the fine uneven structure portion 4 exceeds 10 μm, the resin of the uncured coating film may overflow or wrinkles may be caused during the press-working. When the thickness of the fine uneven structure portion is extremely thin, sufficient molding becomes difficult.
Since moldability varies depending on the shape of the fine uneven structure of the original plate, it is preferable to provide a fine uneven structure portion having a thickness 3 to 10 times the desired depth.
When the fine uneven structure forming portion is formed, it may be formed separately at intervals by a printing method, and particularly if it is a gravure printing method, printing can be performed at low cost. In addition, in order to adjust the coating film thickness, a substance diluted with a solvent may be coated and dried.
In addition, in the molding of the fine uneven structure portion, a polyurethane resin, a melamine resin, a phenol resin, or the like, which is obtained by adding a polyisocyanate as a crosslinking agent to an acrylic polyol, a polyester polyol, or the like having a reactive hydroxyl group and crosslinking the mixture, may be used. As the ultraviolet or electron beam curable resin, epoxy (meth) acrylate, urethane (meth) acrylate, or the like can be used, and the thickness thereof is preferably set to 0.5 μm to 5.0 μm.
In the molding of the fine uneven structure portion, in addition to the above-described resin, a resin material containing a metal such as aluminum or silver, an inorganic oxide such as silica or mica, a magnetic material such as magnetite, or the like can be used.
(landfill site)
In fig. 1 and 2, a filling portion 7 is provided between the fine uneven structure portions 4. When only the pressure-bonding section is peeled from the supporting base material by thermocompression bonding, the buried portion 7 is provided, and even if the fine uneven structure section 4 is formed of a material which is rigid and has low fracture properties, the generation of burrs can be suppressed.
(reflection layer)
In fig. 1 and 2, the material of the reflective layer 5 may be a single metal material such as Al, Sn, Cr, Ni, Cu, Au, or Ag, or a compound thereof. The thickness of the reflective layer is preferably
To
As the reflective layer 5, a transparent material can be used, and examples thereof are listed below. The numerical value in parentheses after the chemical formula or the compound name shown below represents the refractive index n. Examples of the ceramics include: sb2O3(3.0)、Fe2O3(2.7)、TiO2(2.6)、CdS(2.6)、CeO2(2.3)、ZnS(2.3)、PbCl2(2.3)、CdO(2.2)、Sb2O3(5)、WO3(5)、SiO(5)、Si2O3(2.5)、In2O3(2.0)、PbO(2.6)、Ta2O3(2.4)、ZnO(2.1)、ZrO2(5)、MgO(1)、Si2O2(10)、MgF2(4)、CeF3(1)、CaF2(1.3～1.4)、AlF3(1)、Al2O3(1) GaO (2), etc. Examples of organic polymers include: polyethylene (1.51), polypropylene (1.49), polytetrafluoroethylene (1.35), polymethyl methacrylate (1.49), polystyrene (1.60), and the like. These materials are appropriately selected based on optical properties such as refractive index, reflectance and transmittance, weather resistance, interlayer adhesion, and the like, and are formed in the form of a thin film.
As a method for forming the reflective layer 5, known methods such as a vacuum deposition method, a sputtering method, and a CVD method, which can control a film thickness, a film forming speed, the number of stacked layers, an optical film thickness, and the like, can be appropriately used, and in addition, a high-brightness ink in which fine particles of these materials are dispersed in various solvents can be applied.
The high-brightness light-reflecting ink, the organic polymer, or the fine particles of the organic polymer, which are obtained by dispersing the fine powder, sol, or metal nanoparticles of the metal, ceramic, or organic polymer in an organic polymer resin, may also be used. In this case, care should be taken not to corrode the fine uneven structure portion 4 with a solvent, and it can be formed by a known printing method such as a gravure printing method, a flexographic printing method, a screen printing method, or the like. When the reflective layer 5 is provided by such a printing method, the thickness after drying may be adjusted to be about 0.001 μm to 10 μm.
The reflective layer 5 may be partially provided. In this case, a fine island-shaped reflective layer may be provided by vacuum deposition of, for example, tin, in addition to patch processing (パスタ processing), water-washed diatomaceous earth processing (water-washed シーライト processing), laser processing, and the like.
When a transparent reflective layer is provided, the effect of the optical element during transmission can be utilized as long as the transmittance in the wavelength region of 400nm to 700nm is 20% or more. Further, information disposed under the reflective layer, for example, print information such as a photograph, characters, and a pattern can be confirmed.
(mask layer)
In fig. 2, a mask layer 8 covering the reflective layer 5 is provided between the reflective layer 5 and the adhesive layer 6, and the reflective layer 6 may be partially etched away by, for example, immersing the mask layer in an alkaline solution.
For the mask layer 7, for example, a thermoplastic resin such as a polyamide resin, a polyimide resin, or a vinyl resin, or a resist that is cured by ultraviolet rays can be used.
(adhesive layer)
In fig. 1 and 2, the adhesive layer 6 may be made of, for example, a thermoplastic resin such as a polyester resin, an acrylic resin, a vinyl chloride resin, a vinyl resin, a polyamide resin, a polyvinyl acetate resin, a rubber resin, an ethylene-vinyl acetate copolymer resin, or a vinyl chloride-vinyl acetate copolymer resin.
The thermosetting resin can be used as long as it is soft, and examples thereof include a soft epoxy resin, a soft urethane resin, and the like. Flexibility can be imparted to a curable resin even by a method of adding a plasticizer to the curable resin or a method of introducing an elastic structure such as a flexible polyurethane skeleton or rubber into the skeleton of the cured resin.
The index of flexibility includes values such as elongation, tensile stress, and tensile elastic modulus, and if the index is elongation, the elongation measured by the test method of ISO527 using ISO3167 test pieces (100 μm thickness) is preferably 5% or more, and more preferably 20% or more. By covering the fine uneven structure portion 4 with such a soft resin, the impact resistance of the fine uneven structure portion 4 can be improved.
The adhesive layer 6 can be formed by coating the above resin by gravure coating, lip coating, micro gravure coating, or extruder coating.
In addition, the thickness of the adhesive layer 6 is preferably 1 μm to 20 μm.
The visible region may be colored by adding a dye or pigment to any one of the film base 2, the adhesive layer 3, the fine textured portion 4, the reflective layer 5, the mask layer 8, and the adhesive layer 6. Further, a material excited by ultraviolet light or infrared light may be added to impart an effect that can be recognized by visual or mechanical detection in a specific wavelength region.
Next, an example of the method for manufacturing the fine uneven structure portion according to the embodiment will be described with reference to the schematic cross-sectional views shown in fig. 3 and 4.
The molding film 56 for molding the fine textured structure portion is wound off from the molding film winding-off roller 51. As shown in fig. 4, a resin layer having a molding structure having a shape inverted to the fine uneven structure portion shown in fig. 1 and 2 is formed in advance on one surface (lower surface) of the molding film 56. The molding film 56 is passed between the molding resin ink application roller 52 and the molding resin ink pressing roller 53 so that the lower surface thereof is positioned on the application roller 52 side. At this time, as shown in fig. 3, the application roller 52 is rotated while being immersed in the molding resin ink 55 in the molding resin ink holding container 54, and thus the molding resin ink is deposited on one surface (lower surface) of the molding film 56 in a pattern as shown in fig. 4. Therefore, as shown in the same fig. 4, the molding resin ink adhering to the application roller 52 is transferred onto the resin layer of the molding film 56, and an uncured micro uneven structure portion is formed. Thereafter, the molding film 57 on which the fine uneven structure portion is formed is conveyed to the molding resin ink curing portion 58, where the uncured molding resin ink of the fine uneven structure portion is cured to form a film, thereby forming the fine uneven structure portion.
On the other hand, the adhesive film 66 for transferring the fine uneven structure portion is wound from the adhesive film winding-out roller 61 and passed between the adhesive ink application cylinder 62 and the adhesive ink pressurizing cylinder 63. At this time, the application roller 62 is rotated while being immersed in the bonding ink 65 in the bonding ink holding container 64, and the bonding ink adheres to the entire circumferential surface thereof. Therefore, the bonding ink 65 is transferred from the application roller 62 to the bonding film 66, and a bonding ink layer is formed on the bonding film 66. Thereafter, the bonding film 67 on which the bonding ink layer is formed is conveyed to the bonding ink curing unit 68, where the bonding ink layer is cured to form a film.
Next, the forming film 57 on which the fine uneven structure portion is formed and the bonding film 67 on which the bonding ink layer is formed are connected to each other by a pair of bonding rollers 59 and 69, and heated as necessary, whereby the fine uneven structure portion of the forming film 57 is transferred to the bonding ink layer of the bonding film 67. Thereafter, the molding film 56 having the resin layer on which the molding structure is molded is peeled off at the film peeling section 71 in fig. 3, and wound around the take-up roll 60. On the other hand, the bonding film 67 having the fine uneven structure portion transferred to the bonding ink layer is wound around the winding roller 70.
The following describes in detail the material used in the manufacturing method of fig. 3 and 4 and the formation of the fine uneven structure.
(film for Forming)
In fig. 3, as the molding film 56 for molding the fine uneven structure, a film having a resin layer having a molding structure formed by a known method such as an "embossing method", "casting method", or "photopolymer method" on a plastic film such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), or PP (polypropylene) can be used. In the present invention, the resin layer formed with the molding structure is used only for molding of the molding resin ink, and is not provided with metal by deposition processing or the like, and therefore, for example, a silicon compound, a fluorine compound, an inorganic filler, or the like may be added to the resin layer to perform mold release treatment. The resin layer having the molding structure can be formed using a material that does not require adhesion to metals.
(ink curing section)
In fig. 3, the molding resin ink curing section 58 and the bonding ink curing section 68 may be, for example, an oven using heat and air blowing, or an irradiation device using ultraviolet rays or electron beams.
(ink for bonding)
As the bonding ink, a laminating agent formed by hot pressing, a resin material which is cured by irradiation of ultraviolet rays or electron beams and loses its adhesive force, or the like can be used.
According to the transfer laminated medium of the embodiment described above, since the fine uneven structure portions are formed individually and independently at intervals so as to be able to wrap the area to be transferred by hot stamping, the fine uneven structure portions have good fracture properties without being affected by fracture properties such as heat resistance and hardness of the resin used for the fine uneven structure portions, and transfer burrs and transfer defects can be prevented from occurring in the fine uneven structure portions during thermal transfer. Further, since the fine uneven structure portion 4 is covered with the adhesive layer 6, the impact resistance of the fine uneven structure portion 4 can be improved.
The function of the transfer laminated medium will be described in detail below with reference to fig. 5.
The transfer laminated medium 1 has a form in which the adhesive layer 3, the fine uneven structure portion 4, the reflective layer 5, and the adhesive layer 6 are provided in this order on the support base material 2 as described above, and the fine uneven structure portion 4 is formed separately at intervals so as to be included in the region to be transferred by hot stamping, and has a fine uneven shape. When a transfer laminate (in which a fine uneven structure 4 having a fine uneven shape is enclosed) is thermally transferred onto a transfer target (for example, paper) 81 using this transfer lamination medium 1, a stamp 82 shown in the same fig. 5 is pressed from the support base 2 side. The pressing surface (lower surface) of the stamp 82 corresponds to the region to be transferred, and the region to be transferred having a width (e.g., diameter) R includes the fine textured portion 4. As a result, the outer periphery of the region to be transferred is located in the buried portion 7 surrounding the fine textured portion 4, and does not overlap the outer periphery of the fine textured portion 4, so that it is possible to prevent transfer burrs or transfer defects from being directly generated in the fine textured portion 4 during thermal transfer.
The prevention of such transfer flash or transfer defect is more clearly illustrated in fig. 6. That is, in fig. 6, the region corresponding to the region a' in fig. 8 when the conventional transfer laminated medium 101 is not used.
Therefore, a printed matter or the like having a transfer laminate including a fine uneven structure portion formed on a transfer target body can be obtained with high yield.
In addition, according to the transfer laminate medium of the embodiment, a pattern including a fine uneven structure portion in which a resin is molded can be transferred to a transfer target, and the transfer is difficult to be performed by any of the "imprint method", the "casting method", and the "photopolymer method" due to a softening temperature, adhesion to a metal, and the like.
According to the transfer laminate medium of the embodiment, a pattern including a fine uneven structure portion formed with a resin containing a metal, silica, a magnetic material, an inorganic metal oxide, a liquid crystal, or the like can be transferred to a transfer target.
Hereinafter, an embodiment of the present invention will be described with reference to fig. 3.
(example 1)
The film 56 for molding is obtained by coating a polyurethane resin on a PET substrate, drying the resin, and then performing "imprint method". The molding film 56 is wound off from the molding film take-up roll 51, the molding resin ink holding container 54 is filled with a polyamide imide resin as the molding resin ink 55 for forming the fine uneven structure portion, the molding resin ink application drum 52 having a pattern formed thereon is aligned with the molding film 56, the molding resin ink 55 is transferred onto the molding film 56 by being pressurized by the molding resin ink pressurization drum 53, and the molding resin ink is dried in the molding resin ink curing portion 58 using a hot air oven.
On the other hand, a PET substrate coated with a release layer made of an acrylic resin was used for the adhesive film 66, the adhesive film 66 was wound out from the adhesive film take-up roll 61, the adhesive ink holding container 64 for adhesion was filled with the acrylic adhesive resin as the adhesive ink 65, the adhesive ink 65 was transferred to the adhesive film 66 by pressing the adhesive ink pressure roller 63 from the adhesive ink application roller 62 onto the adhesive film 66, and the adhesive ink was dried in the adhesive ink curing section 68 using a hot air oven.
At the contact point between the forming film laminating roller 59 and the laminating film laminating roller 69, the forming film 57 having the fine uneven structure portion and the laminating film 67 having the laminating ink layer formed thereon are pressed and joined to transfer the fine uneven structure to the laminating film side, the forming film 56 and the laminating film 66 are peeled off at the film peeling portion 71, and the laminating film provided with the fine uneven structure portion is wound around the laminating film winding roll 70. On the other hand, the molding film 56 separated from the fine uneven structure portion is wound around a molding film winding roller 60.
Next, the bonding film 66 is laminated on the fine uneven structure portion side
Depositing aluminum metal to form a reflective layer. Next, a mask layer made of a polyamide imide resin is applied only to a desired position of the reflective layer 5, and the mask layer is immersed in a sodium hydroxide solution to selectively remove the reflective layer by etching, thereby forming a patterned reflective layer. After the etching removal, the bonding film 66 is washed with a hydrochloric acid solution and water, and dried with hot air. Thereafter, the adhesive layer 6 made of an acrylic resin is applied to the dried adhesive film 66, and the transfer laminate medium 1 having the fine uneven structure portion formed separately with a space as shown in fig. 2 is manufactured.
The obtained transfer laminated medium was thermally pressed onto cotton paper using a top-bottom type thermal transfer device having a hot stamp, and the adhesive film 66 was peeled off and removed.
The fine textured part is enclosed in the cotton paper, the outer periphery of the area to be transferred is located at a portion surrounding the fine textured part and does not overlap with the outer periphery of the fine textured part, and therefore the transfer laminate containing the fine textured part without generating burrs is thermally transferred to the cotton paper.
Thereafter, a heat resistance test was performed by bringing a 200 ℃ iron into contact with the transfer laminate in which the relief forming layer as the fine textured portion was wrapped on the cotton paper for 30 minutes. As a result, the relief forming layer made of the polyamideimide resin maintains a fine uneven structure without deterioration, discoloration, or peeling.
Comparative example 1-1
The surface of the release layer of the PET substrate was coated with a polyurethane resin, and the fine uneven structure layer was formed by an "imprint method". A reflective layer is formed by depositing aluminum on the fine uneven structure layer, and a mask layer made of a polyamide imide resin is further applied to a desired position and dried. Then, the reflective layer is selectively etched and removed by a sodium hydroxide solution to form a patterned reflective layer. Thereafter, an acrylic resin adhesive is applied to produce a transfer laminate medium having a fine uneven structure portion as a continuous formation layer.
The obtained transfer laminated medium was thermally transferred onto cotton paper using a top-bottom thermal transfer machine having a hot stamp. The transfer laminate with the burrs created was thermally transferred to cotton paper.
Thereafter, a heat resistance test was performed by bringing an iron at 200 ℃ into contact with the transfer laminate having the relief forming layer as the fine uneven structure portion for 30 minutes. As a result, the relief forming layer made of the polyurethane resin discolors and whitens, and the fine uneven structure is deformed.
Comparative examples 1 and 2
A polyamide imide resin was applied to the surface of the release layer of a PET substrate, and molding by an "imprint method" was carried out. As a result, since the polyamideimide resin is a resin having high heat resistance, the fine uneven structure forming layer cannot be formed at a molding temperature of less than 200 ℃. Therefore, the molding temperature is raised to 200 ℃ or higher, and the molding by the "imprint method" is performed, thereby molding the fine uneven structure forming layer on the polyamideimide resin. However, the PET substrate has poor heat resistance, and therefore, shrinkage and deformation occur, and stable molding of the fine uneven structure forming layer is difficult.
Then, forming a layer surface on the fine uneven structure to
Depositing aluminum metal to form a reflective layer. Next, a mask layer made of a polyamide imide resin is applied only to a desired position of the reflective layer, and the reflective layer is selectively etched and removed by immersing the mask layer in a sodium hydroxide solution, thereby forming a patterned reflective layer. After the etching removal, the PET substrate was washed with a hydrochloric acid solution and water, and dried with hot air. Thereafter, an adhesive layer made of an acrylic resin was applied to the dried PET substrate, thereby producing a transfer laminate medium having a fine uneven structure portion as a continuous layer.
The obtained transfer laminated medium was thermally transferred onto cotton paper using a top-bottom thermal transfer machine having a hot stamp. As a result, the forming layer for forming the fine uneven structure is made of a hard polyamide imide resin, and therefore, burrs are generated around the fine uneven structure portion of the transfer laminate.
Comparative examples 1 to 3
A transfer laminate medium was produced by the same production method using the same material as in comparative example 1, except that a polyamide imide resin having a Tg of 260 ℃, a breaking elongation of less than 10%, low flexibility and brittleness was used as the fine uneven layer, and the fine uneven layer was applied to the entire surface of the molding film.
The obtained transfer laminated medium has a fine uneven layer formed on the entire surface.
The obtained transfer laminated medium was thermally transferred onto cotton paper using a top-bottom thermal transfer machine having a hot stamp. As a result, the layer forming the fine uneven structure is made of a hard and brittle polyamide imide resin, and therefore, cracks are generated in the fine uneven structure portion of the transfer laminate.
(example 2)
The film 56 for molding is obtained by coating a polyurethane resin on a PET substrate, drying the resin, and then performing "imprint method". The molding resin ink holding container 54 is filled with an aluminum-containing acrylic resin as a molding resin ink 55 for forming a fine uneven structure portion, the molding resin ink applying drum 52 having a pattern formed thereon is aligned with the molding film 56 and pressurized by the molding resin ink pressurizing drum 53, so that the molding resin ink 55 is transferred onto the molding film 56, and the molding resin ink is dried in the molding resin ink curing portion 58 using a hot air oven.
On the other hand, a PET substrate coated with a release layer made of an acrylic resin was used for the adhesive film 66, the adhesive film 66 was wound out from the adhesive film take-up roll 61, the adhesive ink holding container 64 was filled with the acrylic adhesive resin used as the adhesive ink 65, the adhesive ink 65 was transferred to the adhesive film 66 by pressing the adhesive ink pressure roller 63 from the adhesive ink application roller 62 onto the adhesive film 66, and the adhesive ink was dried in the adhesive ink curing section 68 using a hot air oven.
At the contact point between the forming film laminating roller 59 and the laminating film laminating roller 69, the forming film 57 having the fine uneven structure portion and the laminating film 67 having the laminating ink layer formed thereon are pressed and bonded, the fine uneven structure is transferred to the laminating film side, the forming film 56 and the laminating film 66 are peeled off at the film peeling portion 71, and the laminating film provided with the fine uneven structure portion is wound around the laminating film winding roll 70. On the other hand, the molding film 56 separated from the fine uneven structure portion is wound around a molding film winding roller 60.
Next, an adhesive layer made of an acrylic resin is applied to the fine uneven structure portion side of the bonding film 66, and the transfer laminate medium 1 having the fine uneven structure portion formed separately with a space as shown in fig. 1 is manufactured.
The obtained transfer laminated medium was thermally pressed onto cotton paper using a top-bottom type thermal transfer device having a hot stamp, and the adhesive film 66 was peeled off and removed.
The fine textured part is enclosed in the cotton paper, the outer periphery of the area to be transferred is located at a portion surrounding the fine textured part and does not overlap with the outer periphery of the fine textured part, and therefore the transfer laminate containing the fine textured part without generating burrs is thermally transferred to the cotton paper.
Although the transfer-use laminated medium was not subjected to formation of a reflective layer by deposition, it was confirmed that: the aluminum contained in the fine textured portion functions as a reflective layer, and the fine textured portion emits diffracted light.
Comparative example 2
An aluminum-containing acrylic resin similar to that of example 2 was applied to the surface of the release layer of the PET substrate, and the release layer was molded by the "imprint method". As a result, since the aluminum-containing acrylic resin has high rigidity, the fine uneven structure forming layer cannot be formed at a forming temperature of less than 200 ℃. Therefore, the temperature is raised to 200 ℃ or higher and the molding is performed by the "imprint method", and the fine uneven structure forming layer is formed on the aluminum-containing acrylic resin. However, the PET substrate has poor heat resistance, and therefore, shrinkage and deformation occur, and stable molding of the fine uneven structure forming layer is difficult.
Next, an adhesive layer made of an acrylic resin was applied to the fine uneven structure forming layer side of the PET substrate, and a transfer laminate medium having a fine uneven structure portion as a continuous forming layer was produced.
The obtained transfer laminated medium was thermally transferred onto cotton paper using a top-bottom thermal transfer machine having a hot stamp. As a result, since the formation layer for forming the fine uneven structure is made of a hard acrylic resin containing aluminum, burrs are generated around the fine uneven structure portion of the transfer laminate.
(example 3)
The film 56 for molding is obtained by coating a polyurethane resin on a PET substrate, drying the resin, and then performing "imprint method". The molding film 56 is wound off from the molding film winding-off roll 51, the molding resin ink holding container 54 is filled with melamine resin as the molding resin ink 55 for forming the fine uneven structure portion, the molding resin ink application drum 52 having the pattern formed thereon is aligned with the molding film 56, the molding resin ink 55 is transferred onto the molding film 56 by being pressurized by the molding resin ink pressurization drum 53, and the molding resin ink is dried in the molding resin ink curing portion 58 using a hot air oven.
On the other hand, a PET substrate coated with a release layer made of an acrylic resin was used for the adhesive film 66, the adhesive film 66 was wound out from the adhesive film take-up roll 61, the adhesive ink holding container 64 for adhesion was filled with the acrylic adhesive resin as the adhesive ink 65, the adhesive ink 65 was transferred to the adhesive film 66 by pressing the adhesive ink pressure roller 63 from the adhesive ink application roller 62 onto the adhesive film 66, and the adhesive ink was dried in the adhesive ink curing section 68 using a hot air oven.
At the contact point between the forming film laminating roller 59 and the laminating film laminating roller 69, the forming film 57 having the fine uneven structure portion and the laminating film 67 having the laminating ink layer formed thereon are pressed and joined to transfer the fine uneven structure to the laminating film side, the forming film 56 and the laminating film 66 are peeled off at the film peeling portion 71, and the laminating film provided with the fine uneven structure portion is wound around the laminating film winding roll 70. On the other hand, the molding film 56 separated from the fine uneven structure portion is wound around a molding film winding roller 60.
Next, the bonding film 66 is laminated on the fine uneven structure portion side
Depositing aluminum metal to form a reflective layer. Next, a mask layer made of a polyamide imide resin is applied only to a desired position of the reflective layer 5, and the mask layer is immersed in a sodium hydroxide solution to selectively remove the reflective layer by etching, thereby forming a patterned reflective layer. After the etching removal, the bonding film 66 is washed with a hydrochloric acid solution and water, and dried with hot air. Thereafter, the adhesive layer 6 made of an acrylic resin is applied to the dried adhesive film 66, and the transfer laminate medium 1 having the fine uneven structure portion formed separately with a space as shown in fig. 2 is manufactured.
The obtained transfer laminated medium was thermally pressed onto cotton paper using a top-bottom type thermal transfer device having a hot stamp, and the adhesive film 66 was peeled off and removed.
The fine textured part is enclosed in the cotton paper, the outer periphery of the area to be transferred is located at a portion surrounding the fine textured part and does not overlap with the outer periphery of the fine textured part, and therefore the transfer laminate containing the fine textured part without generating burrs is thermally transferred to the cotton paper.
Thereafter, a heat resistance test was performed by bringing a 200 ℃ iron into contact with the transfer laminate in which the relief forming layer as the fine textured portion was wrapped on the cotton paper for 30 minutes. As a result, the relief forming layer made of melamine resin does not change in quality, change in color, or peel off, and retains a fine uneven structure.
Comparative example 3
The surface of the release layer of the PET substrate was coated with melamine resin and molded by the "imprint method". As a result, since the melamine resin is a resin having high heat resistance, the fine uneven structure forming layer cannot be molded at a temperature lower than 300 ℃. Therefore, the molding temperature is raised to 300 ℃ or higher, and the fine uneven structure forming layer is molded on the melamine resin by the "imprint method". However, the PET substrate has poor heat resistance, and therefore, shrinkage and deformation occur, and stable molding of the fine uneven structure forming layer is difficult.
Then, forming a layer surface on the fine uneven structure to
Depositing aluminum metal to form a reflective layer. Next, a mask layer made of a polyamide imide resin is applied only to a desired position of the reflective layer, and the reflective layer is selectively etched and removed by immersing the mask layer in a sodium hydroxide solution, thereby forming a patterned reflective layer. After the etching removal, the PET substrate was washed with a hydrochloric acid solution and water, and dried with hot air. Thereafter, an adhesive layer made of an acrylic resin was applied to the dried PET substrate, thereby producing a transfer laminate medium having a fine uneven structure portion as a continuous layer.
The obtained transfer laminated medium was thermally transferred onto cotton paper using a top-bottom thermal transfer machine having a hot stamp. As a result, since the forming layer for forming the fine uneven structure is made of a rigid and brittle melamine resin, burrs are generated around the fine uneven structure portion of the transfer laminate.
(example 4)
The film 56 for molding is obtained by coating a polyurethane resin on a PET substrate, drying the resin, and then performing "imprint method". The molding resin ink holding container 54 is filled with a titanium dioxide-containing acrylic resin as a molding resin ink 55 for forming a fine uneven structure portion, the molding resin ink applying drum 52 having a pattern formed thereon is aligned with the molding film 56 and pressurized by the molding resin ink pressurizing drum 53, so that the molding resin ink 55 is transferred onto the molding film 56, and the molding resin ink is dried in the molding resin ink curing portion 58 using a hot air oven.
On the other hand, a PET substrate coated with a release layer made of an acrylic resin was used for the adhesive film 66, the adhesive film 66 was wound out from the adhesive film take-up roll 61, the adhesive ink holding container 64 was filled with the acrylic adhesive resin used as the adhesive ink 65, the adhesive ink 65 was transferred to the adhesive film 66 by pressing the adhesive ink pressure roller 63 from the adhesive ink application roller 62 onto the adhesive film 66, and the adhesive ink was dried in the adhesive ink curing section 68 using a hot air oven.
At the contact point between the forming film laminating roller 59 and the laminating film laminating roller 69, the forming film 57 having the fine uneven structure portion and the laminating film 67 having the laminating ink layer formed thereon are pressed and bonded, the fine uneven structure is transferred to the laminating film side, the forming film 56 and the laminating film 66 are peeled off at the film peeling portion 71, and the laminating film provided with the fine uneven structure portion is wound around the laminating film winding roll 70. On the other hand, the molding film 56 separated from the fine uneven structure portion is wound around a molding film winding roller 60.
Next, an adhesive layer made of an acrylic resin is applied to the fine uneven structure portion side of the bonding film 66, and the transfer laminate medium 1 having the fine uneven structure portion formed separately with a space as shown in fig. 1 is manufactured.
The obtained transfer laminated medium was thermally pressed onto cotton paper using a top-bottom type thermal transfer device having a hot stamp, and the adhesive film 66 was peeled off and removed.
The fine textured part is enclosed in the cotton paper, the outer periphery of the area to be transferred is located at a portion surrounding the fine textured part and does not overlap with the outer periphery of the fine textured part, and therefore the transfer laminate containing the fine textured part without generating burrs is thermally transferred to the cotton paper.
Although the transfer-use laminated medium was not subjected to formation of a reflective layer by deposition, it was confirmed that: the titanium dioxide contained in the fine textured portion functions as a reflective layer, and the fine textured portion emits diffracted light.
Comparative example 4
The same titanium dioxide-containing acrylic resin as in example 2 was applied to the surface of the release layer of the PET substrate, and the release layer was molded by the "embossing method". As a result, since the titanium dioxide-containing acrylic resin is a resin having high rigidity, the fine uneven structure forming layer cannot be formed at a forming temperature of less than 200 ℃. Therefore, the temperature is raised to 200 ℃ or higher and the resulting product is molded by the "imprint method", and the fine uneven structure forming layer is molded on the titanium dioxide-containing acrylic resin. However, the PET substrate has poor heat resistance, and therefore, shrinkage and deformation occur, and stable molding of the fine uneven structure forming layer is difficult.
Next, an adhesive layer made of an acrylic resin was applied to the fine uneven structure forming layer side of the PET substrate, thereby producing a transfer laminated medium.
The obtained transfer laminated medium was thermally transferred onto cotton paper using a top-bottom thermal transfer machine having a hot stamp. As a result, the forming layer for forming the fine uneven structure is made of a hard acrylic resin containing titanium dioxide, and therefore, burrs are generated around the fine uneven structure portion of the transfer laminate.
Although the details of the respective members have been described above with reference to the examples, the present invention can be suitably used for the purpose of use, for example, of performing printing on the surface or between layers, or performing a protective layer to reduce the height difference between arbitrary layers provided in a pattern. In consideration of the adhesiveness of the layers, an adhesion anchor layer may be provided between the layers, or various easy adhesion treatments such as corona discharge treatment, plasma treatment, and flame treatment may be performed.
Industrial applicability
According to the present invention, a transfer laminate medium can be provided in which a fine uneven structure portion used in a fresnel lens sheet or a lenticular lens sheet used in a relief hologram, a diffraction grating, a sub-wavelength grating, a microlens, a polarizing element, a fluorescent screen, or the like, a backlight and a diffusion sheet of a liquid crystal device, an antireflection film, or the like is included in a region to be transferred, using a material that is difficult to form by a "imprint method", "casting method", or "photopolymer method".
Further, by thermally transferring the transfer laminate medium of the present invention to a transfer target body by hot stamping, various industrially useful printed matters and the like having a transfer laminate including a fine uneven structure portion without generating burrs can be obtained at a good yield. Can be used as a fine uneven structure for industrial use.
Description of the symbols
1 … transfer laminate medium, 2 … support base material, 3 … adhesive layer, 4 … fine uneven structure portion, 5 … reflective layer, 6 … adhesive layer, 7 … buried portion, 8 … mask layer, 51 … forming film take-up roller, 52 … forming resin ink application roller, 53 … forming resin ink pressurization roller, 54 … forming resin ink holding container, 55 … forming resin ink, 56 … forming film, 57 … forming film with fine uneven structure portion, 58 … forming resin ink curing portion, 59 … forming film bonding roller, 60 … forming film take-up roller, 61 … adhesive film take-up roller, 62 … adhesive ink application roller, 63 … adhesive ink pressurization roller, 64 … adhesive ink holding container, 65 … adhesive ink, 66 … adhesive film, 67 … adhesive film with ink layer, 3668 adhesive ink curing portion, 68 … adhesive ink curing portion, 69 … roll for sticking a sticking film, 70 … roll for winding a sticking film, 71 … film peeling section, 81 … transferred object, 82 … hot stamping, 101 … transfer laminated medium, 102 … support base material, 103 … sticking layer, 104 … fine uneven structure forming layer, 105 … reflective layer, 106 … adhesive layer.
Claims (9)
1. A transfer laminate medium for forming a transfer laminate having a fine uneven structure portion having a fine uneven shape enclosed therein on a transfer object by hot stamping, comprising:
a supporting substrate,
A bonding layer formed on the supporting substrate,
A fine uneven structure portion having a fine uneven shape on the adhesive layer, and
an adhesive layer formed on the fine uneven structure portion, wherein,
the fine uneven structure portions are formed separately at intervals so as to be enclosed in the region to be transferred by hot stamping,
the fine uneven structure portion is formed separately at intervals by a printing method.
2. The transfer laminate medium according to claim 1,
a buried portion is provided between the fine uneven structure portions formed separately, and the buried portion is made of the same material as the adhesive layer.
3. The transfer laminate medium according to claim 1,
the adhesive layer is made of a flexible resin having an elongation of 5% or more as measured by a test method of ISO527 using an ISO test piece (100 μm thick).
4. The transfer laminate medium according to claim 1,
the fine textured portion is made of a heat-resistant resin material having a glass transition temperature of 200 ℃ or higher.
5. The transfer laminate medium according to claim 1,
the fine textured portion is made of a resin material containing an organic nitrogen compound.
6. The transfer laminate medium according to claim 1,
the fine textured portion is made of a resin material containing metal particles.
7. The transfer laminate medium according to claim 1,
the fine textured portion is made of a resin material containing metal oxide particles.
8. The transfer laminate medium according to claim 1,
the printing method is a gravure printing method.
9. A printed matter having a transfer laminate comprising a fine uneven structure having a fine uneven shape, characterized in that,
at least the fine uneven structure in the transfer laminate is formed by transferring the transfer laminate medium according to any one of claims 1 to 8 onto a transfer object by hot stamping,
the micro concavo-convex structure body is enclosed in an area to be transfer-printed by hot stamping.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-116271 | 2013-05-31 | ||
| JP2013116271 | 2013-05-31 | ||
| CN201480030804.4A CN105246705A (en) | 2013-05-31 | 2014-05-30 | Layering medium for transfer and printed matter |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480030804.4A Division CN105246705A (en) | 2013-05-31 | 2014-05-30 | Layering medium for transfer and printed matter |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111675978A true CN111675978A (en) | 2020-09-18 |
Family
ID=51988365
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010529196.9A Pending CN111675978A (en) | 2013-05-31 | 2014-05-30 | Transfer laminated medium and printed matter |
| CN201480030804.4A Pending CN105246705A (en) | 2013-05-31 | 2014-05-30 | Layering medium for transfer and printed matter |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480030804.4A Pending CN105246705A (en) | 2013-05-31 | 2014-05-30 | Layering medium for transfer and printed matter |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US10059086B2 (en) |
| EP (1) | EP3006225A4 (en) |
| JP (1) | JP6354753B2 (en) |
| CN (2) | CN111675978A (en) |
| WO (1) | WO2014192314A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112987158A (en) * | 2021-04-09 | 2021-06-18 | 广东晟铂纳新材料科技有限公司 | Iron-based optically variable pigment and manufacturing method and application thereof |
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| DE112017000519T5 (en) * | 2016-01-27 | 2018-10-25 | Toppan Printing Co., Ltd. | LAYER, METHOD FOR MAKING A LAYER AND PERSONAL AUTHENTICATION MEDIUM |
| KR102219468B1 (en) * | 2016-09-23 | 2021-02-25 | 다이니폰 인사츠 가부시키가이샤 | Thermal transfer sheet, manufacturing method of print, and game machine |
| EP3366474B1 (en) * | 2017-02-22 | 2020-06-24 | KBA-NotaSys SA | Printing press with in-line casting device for the replication and formation of a micro-optical structure |
| CN109109550A (en) * | 2018-08-17 | 2019-01-01 | Oppo广东移动通信有限公司 | Processing method, housing unit and the electronic equipment of housing unit |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2014192314A1 (en) | 2017-02-23 |
| WO2014192314A1 (en) | 2014-12-04 |
| US10059086B2 (en) | 2018-08-28 |
| EP3006225A1 (en) | 2016-04-13 |
| JP6354753B2 (en) | 2018-07-11 |
| EP3006225A4 (en) | 2017-01-11 |
| US20160107430A1 (en) | 2016-04-21 |
| CN105246705A (en) | 2016-01-13 |
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Application publication date: 20200918 |